Reaction products of nitriles



Patented Oct. 28, 1952 UNITED STATES PATENT OFFICE REACTION PRODUCTS OF NITRILES Ernst Zerner and Mark W. Pollock, New York, N. Y., assignors to Sun Chemical Corporation, New York, N. Y., a corporation of Delaware No Drawing. Original application June 10, 1948, Serial No. 32,263. Divided and this application June 27, 1951, Serial No. 233,933

7 Claims.

where R. represents substituted or unsubstituted open chain hydrocarbon radicals. One of the materials described in the above identified copending application is hexahydro-1,3,5-triacrylyl-s-triazine. Also there is described in this copending application hexahydro-1,3,5-trimethacrylyl-s-triazine.

We have found according to the present invenwhere R3 is a radical which is selected from the group consisting of -CA:CHA where A is selected from the group consisting of hydrogen, halogen and lower alkyl radicals and addition products of CA:CHA and where Ri'is an addition product of CA:CHA.

Of these materials those which contain one or two vinyl groups present in the molecule of the products may be further treated to effect 'polymerization of this material, either alone oraclmixed with other polymerizable monomers to furnish valuable resinous materials which may be employed in various arts in which such materials find application, for instance, as coating materials for paper, wood, metal and cloth, in conjunction with drying oils, and the like.

The polymerized materials, described and claimed in a copending application, Serial No. 32,264, filed June 10, 1948 in the names of Ernst Zerner, Marcel Gradsten and Fred W. West, may be described as polymerization products of compounds ,of the general formula where R1 represents the radical -CI-I:CH2 where A is selected from the group consisting of hydrogen, halogen and lower alkyl radicals where R2 is a radical selected from the group consisting of -CA:CH2 and addition products of --CA:CH2.

As described in the above identified copending application Serial No. 16,135, hexahydro-l,3,5- triacrylyl-s-triazine satisfactorily may be prepared as follows: In a suitable reaction vessel provided with a stirrer, reflux condenser, thermometer and a dropping funnel are placed 265 parts by weight of acrylonitrile dissolved in 400 parts by weight of benzene, together with 2.8 parts of concentrated sulfuric acid. In the dropping funnel is placed a solution of parts by weight of trioxane dissolved in 400 parts by Weight of benzene. The acrylonitrile solution is warmed, satisfactorily on a boiling water bath, and the material in the dropping funnel added at a rate such that the mixture is maintained under reflux conditions. When all of the solution in the dropping funnel has been added, the resulting admixture is heated under reflux conditions for an additional period of approximately three hours. Subsequently the mixture, which contains a yellow precipitate, is allowed to stand overnight and the precipitate then separated by filtration and subsequently recrystallized from ethanol.-

As described in the above identified copending application, Serial No. 16,135, similar products may be obtained using as starting materials ni- H2 CH2 0 H (lg weeks-N r assess:

whose ChQIiQQtQIILSQllCS will be dependent in part where A is hydrogen, halogen or a lower alkyl 7 radical. polymerization reactions either alone or admixed with other polymerizable monomers to form valuable resinous reaction products.

Illustrative of the preparation of such polymer materials are the following examples.

Exampl I:

A solution containing 6 per cent of hexahydro- 13,5-triacrylyls-triazine in per cent acetic acid is heated to boiling. Upon such heattreatment a polymerv material is precipitated from solution and may beseparated therefrom for further utilization.

In the above preparation the rate of formation of the polymer material'can be increased by utilization of a peroxide in the reaction solution.

Example]! A 5 per cent solution of hexahydro-l,3,5-triacrylyl-s-triazine in chloroform together with 0.1 per cent of benzoyl peroxide, based on the triazine, is warmed to effect evaporation of the chloroform and subsequently heated for a period of approximately hour at a temperature of 130 C. in a suitable container. A'brittle white, insoluble polymer materialis secured.

Polymerization of such materialsmay alsobe efiected, for example, in the presence of a, textile material in which case a product is obtained which comprises the textile Inaterialimpregnated with the resinous product.

Also, as above set forth, ccpolymerization may be efiected, as illustratively set forth in thefollowing example.

' EmampleHI A mixture containing 99.65;. percent by weight of styrene, O.25.per cent by Weight ofhexahydro- 1,3,5-triacrylyl-s-triazine and 0.1.per cent .of hen;- zoyl peroxide is heatedv to.60? C. to effect formation of a polymer material. The rate-of polymerization is muchmore rapid with. the triazinepresent than in its absence, and the product obtained is a cross linked polymer, as. distinguishedfrom linear polymers. which are obtained by. the polymerization of styrene- Evidence forthis is the fact that the copolymerization product is in soluble in xylol, whereas polymers of styrene are soluble in such solvent.

Another aspect is the preparation of addition products of tria-zinesofthe type described above in which one, twoor three of the vinyl groups present are converted into saturated groupings by suitable reaction. Avariety of different materials can be employed to react with the vinyl groups presentin thetriazines to addthereto and Such materials may be subjected to to form saturated vinyl groupings. Illustrative of some of the materials which will react are com-- pounds such as sodium bisulfite, alcohols, halo gens, conjugated diolefins, amines, compounds having an active hydrogen, hydrogen sulfide and mercaptans.

Where the above illustrative materials are employed to efiect reaction with triazines containing vinyl groups, either one, two or three 01 the groups rnay be saturated, depending upon the amount of reacting materials utilized. Where only one or two of the vinyl groups is thus saturated, the resulting material may be polymerized, either alone or in conjunction with other polymerizable monomers to form a resinous product.

upon, the modifying reacting material employed to'effect saturation of the vinyl groupings prior to. polymerization, as described and claimed in the said copending application Serial No. 32,264. Illustrative examples setting forth this aspect include the following.

Example I V- 20 parts by weight of hexahydro,.1,3,5,-triacrylyl-s-triazine isdissolved in 500 parts; of wateratapproximately 75 C. When solution is completed there is added thereto 8.2 parts by weight of sodium bisulfite which corresponds to one molecular equivalent of sodium bisulfite per mol of triazine. Addition of the bisulfite is effected while maintaining the solution under agitation conditions When addition of the bisulfite is completed the admixture is cooled and may be filtered to, remove traces of impurities. A slightly milky solutionresults. Upon drying of this solution under vacuum conditions, there is obtained-sals itesel d which is ea soluble e f. an 1 .3 1 35 e t. decpmpose ti eraiurss 111 25 Y Example V,

Aqueous solutions of the productof Example IV; upon treatment with 30'per cent hydrogen peroxide solution polymerized to give a resinous Pro ct.

sa r e A 5-6 per cent solution of the product of Example IV in water, together with two drops of 30' per cent hydrogen peroxide per parts by weight of solution was heated at boiling for ten minutes. The resulting solution was cooled and was employed in normal padding operation to effect impregnation of percale. After padding was completed, the impregnated percale was dried at 100 C. The treated material was remarkably stifier than the original untreated goods, such effect being caused by the polymerization of the sodium bisulfite addition product of hexahydro- 1,3,S-triacrylyl-s-triazine in situ in the fabric material.

Example VII 20 parts by Weight, of hexahydro-1,3,5-triacrylyl-s-triazine is dissolved in 500 parts by weight of waterat 75. C. When solution is completed there is added, with agitation, 16/} parts by weightof sodium bisulfite, corresponding to two molecular-equivalentsof sodium bisulfite p ol. of r a ins- A t r ad t of he b sulfite is completed, the admixtureiscooledand l ere o em m tie pon. drying i -t filtrate under vacuum condition, a clear white water-soluble productsecured which doegnot m l a mn ratur su o-259 C Example VIII Polymerization of the product of Example VII is obtained by dissolving the product in water and treating the aqueous solution with 30 per cent hydrogen peroxide.

Example IX Hexahydro-1,3,5-triacrylyl-s-triazine is treated as described in Example VII except that there is used 24.6 parts by weight of sodium bisulfite corresponding to three molecular equivalents of sodium bisulfite per mol of triazine. A water soluble product is secured which does not undergo polymerization.

Example X parts by weight of hexahydro-1,3,5-triacrylyl-s-triazine is dissolved in 200 parts of chloroform in a reaction vessel equipped with stirring device, thermometer, dropping funnel and reflux condenser. There is then added drop-wise a solution of 0.4 parts by weight of metallic sodium dissolved in 12 parts of n-butanol. Upon completion of this addition the admixture is stirred for a length of time sufficient to complete the reaction, which with the quantities above described is approximately 8 hours. At the end of this reaction period the mixture is made acidic by addition of glacial acetic acid thereto. The reaction admixture is then diluted with 1%; times its volume of ether and filtered. The filtrate is evaporated to remove ether and chloroform and the residue washed with water and then dissolved in ether. The ether solution is dried, satisfactorily with sodium sulfate, and then filtered. To remove ether the admixture is distilled under reduced pressure. A brown viscous oil, the butyl alcohol addition product of hexahydro-1,3,5- triacrylyl-s-triazine is obtained.

The product, upon heating together with benzoyl peroxide, forms a resinous product.

Hexahydro-1,3,5-triacrylyl-s-triazine may be chlorinated by bubbling chlorine into the material in the presence of a small amount of a polymerization inhibitor such as hydroquinone in an amount sufficient to effect saturation of one, two or three of the vinyl groups present. The course of the reaction may be determined by the increase in weight of the reaction admixture at intervals. Where chlorination is discontinued at a point where less than all of the vinyl groups are saturated, a pro-duct is obtained which may be polymerized. Polymerization satisfactorily is effected in the presence of a peroxide polymerization catalyst.

Example XI I-Iexahydro-1,3,5-triacrylyl-s-triazine may be reacted with conjugated diolefins such as butadiene in which case the reaction which occurs appears to involve the formation of a cyclic compound by a 1,4 addition of the vinyl group to the conjugated diolefin. Where less than all of the vinyl groups present are saturated, a product is obtained which may be polymerized. One satisfactory method of effecting such reaction is illustrated in a prior granted patent which shows the reaction between acrylonitrile and conjugated diolefins, namely U. S. P. No. 2,217,632, dated October 8, 1940.

Example XII In a suitable reaction vessel were placed 50 parts of chloroform and 125 parts by weight of hexahydro-1,3,5-triacrylyl-s-triazine. The mixture is warmed until solution is completed, then 6 cooled to room temperature and there is then added thereto, in small portions, 8 parts by weight of decyl amine at a rate such that the temperature of the admixture does not rise above approximately 37" C. After addition of the amine is completed, the reaction admixture is stirred for a period of time sufficient to insure completion of the reaction which with the quantities above described is approximately 1.25 hours. The mixture then may be allowed to stand for several hours and subsequently is filtered and the chloroform removed therefrom by distillation under reduced pressure. A clear viscous liquid material is obtained.

Example XIII Polymerization of the product of Example XII may be secured either in the presence of a peroxide oxidation catalyst or, in the absence of a catalyst, over a somewhat longer period of time. The product which is obtained by polymerization is insoluble in ordinary organic solvents indicating that the process'of polymerization includes cross-linking of the polymers and that the product is not a simple linear polymer.

Example XIV Following the procedure described in Example XII and utilizing 16 parts by weight of decyl amine there is secured an addition product in which two of the three vinyl groups of the triazines have been saturated. This product polymerizes at a rate slower than the product of Example XIII and serves satisfactorily as a plasticizing polymer to be used in conjunction with the polymer of Example XIII.

Example XV In a reaction vessel are placed 50 parts of chloroform and 12.5 parts by weight of hexahydro-1,3,5-triacrylyl-s-triazine and there is then added thereto with stirring 3.65 parts by weight of diethyl amine dissolved in 10 parts of chloroform. After agitation is completed, the admixture is stirred for approximately 2 hours, stirring then discontinued and the mixture allowed to stand for several hours. It then is filtered and the filtrate evaporated under reduced pressure to remove the chloroform. A white solid product is obtained which may be crystallized from ethanol to give a product which softens at C. and melts at C. Recrystallization of this product from toluene gives a material which softens at 146 C. and melts at 149 C.

The product of this reaction, which has only one of the vinyl groups of the triazine saturated, is polymerizable under the general conditions set forth in previous examples.

Example XVI The procedure described in Example XV is followed except that there is used 8 parts by weight of diethyl amine to give a product which is an addition product containing two molecular equivalents of diethyl amine per mol of triazine. The product is water-soluble and is a surface active material.

Example XVII The procedure described in Example XV is followed except that there is utilized 12 parts by weight of diethyl amine to give a reaction product containing three molecular equivalents of diethyl amine per mol of triazine.

Products in which the triazines of the present invention are reacted with materials containing an active hydrogen such as fluorene may be prepared by the utilization of alkaline condensing agents. Illustrations of'suchrreactions. involving nitrile. materials areset. frth, in. U, S'- P; Nil, 2,280,058 of Ami-121;, 1942-.

Illustrations of reaction conditions which; may be employed to effect saturation of the. vinyl. groups oftriazines of the present. invention with materials such as hydrogen, sulfide are setforth; in U. S. P. No. 2,163,176- dated June, 20, 1939.

While the above described products constitute preferred embodiments of the invention, changesv may be made therein without departingfrom the.

scope of the invention, as defined. in the appended: claims.

What is claimed is:

1. As a new produciza compound of the formula where A is selected from thegroup consisting of hydrogen, halogen and lower alkyl radicals,, and- Where Y is selected from the:- group. consisting of SOs-alkali metal, radicals.

As a newproduct; a compound of. theformula;

oxy-alk-yl and aminQ-alkyl' I Q Y\GH2 C Ha- H27- 0 Hr-Y H2. where Y represents; an amino-alkylradical,

3-. As a new product, acompound ofitheformula where Y represents an amino-alkyl radical.

4. As a new product-,acompound of the formula 5. As a new product, a compound of the formula G2H5 5H,

6. Asa new product, a compound of the formula.

MARK W. POLLOCK.

REFERENCES CITED The following references are of record in the 65 fileof this" patent:

UNITED STATESv PATENTS Number Name Date 2,559,835 Zerner July 10, 1951 7 2,568,620. Gresham Sept. 18, 1951 

1. AS A NEW PRODUCT, A COMPOUND OF THE FORMULA 